DE2120370A1 - Process for polymerizing or interpolymerizing vicinal alkylene oxides - Google Patents

Description

Process for polymerizing or interpolymerizing of vlcinal alkylene oxides

The present invention provides a catalyst for polymerizing of vicinal alkylene oxides, which have a high catalytic Activity for a wide variety of vicinal alkylene oxides and excellent stability, which is useful in the manufacture, during storage and when used in a polyno-

rization system is easy to use and is able to handle the Accelerate polymerization at relatively low temperatures and when using a lower catalytic amount, than it is with conventional catalysts of the Pail, so that one polymer having the desired molecular weight and a widely varying crystallinity, for example from an amorphous to a crystalline state. The present invention also relates to a method for Polymerization of vicinal alkylene oxides using this catalyst.

The present invention relates in particular to a process for the polymerization or copolymerization of vicinal alkylene oxides to the corresponding homopolymers or copolymers in the presence of a catalyst which is characterized by that the reaction is carried out in the presence of a catalyst

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which is the reaction product of the following Reactants I and II represents, i.e. the reaction product of at least one of the following reactants I of Formulas (i) to (iii):

I. Aluminum compounds of the formula

wherein R is an alkyl radical having preferably 1-8 carbon atoms, in particular 1-4 carbon atoms, an alkoxy radical with preferably 1-8 carbon atoms, more preferably 1-6 carbon atoms and most preferably 1-4 carbon atoms, and aryl radicals, preferably a phenyl radical, X a halogen atom, preferably a chlorine, bromine or iodine atom, and η is an integer from 0 to 5, metal compounds of group IV of the formula

^R 'm ^MX 4-m <">

where M is a metal of group IV of the periodic table with atomic numbers of 14-72 (Ti, Zr, Hf, Si, Ge and Sn) and when M is a metal of group IVa (typical elements), R 'represents an alkyl radical with preferably 1-8 carbon atoms, more preferably 1-4 carbon atoms, an alkenyl radical. with preferably 1-8 carbon atoms, more preferably 1-4 carbon atoms, an alkoxy radical with preferably 1-8 carbon atoms, more preferably 1-6 carbon atoms and most preferably 1-4 carbon atoms, an aryl radical, preferably a phenyl radical or an aralkyl radical, preferably the benzyl radical and when M represents a Group IVb transition metal, R ^{1 represents} an alkoxy radical and X represents a halogen atom, preferably a chlorine, bromine or iodine atom; and m is an integer from 0-4;

and tin dihalides of the formula

(iii)

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wherein X is a halogen atom, preferably a chlorine or bromine atom, with at least one of the reactants II from the phosphorus-containing compounds of the following 12 groups:

II. 1) (R ¹ O) ₅ PO (1)

wherein R "is a hydrogen atom, an alkyl radical with 1-12 Carbon atoms, preferably 2-8 carbon atoms, a halogenated alkyl radical with 1-12 carbon atoms, preferably 2-4 carbon atoms, an alkenyl radical with 1-12 carbon atoms, preferably 2-4 carbon atoms, or a cycloalkyl radical with 5-7 carbon atoms which has an alkyl or alkenyl side chain with 1-4 May have carbon atoms, where at least one of the groups R "is an organic radical of the above groups and the other groups R "can be identical or different,

2) Z (R ¹¹ O) ₂ PO (2)

wherein R "has the same meaning as that given in the above formula (1), and Z has an alkyl group 1-8 carbon atoms, preferably 1-6 carbon atoms or an ary! Group, preferably the phenyl group,

3) Z ₂ (R "'O) PO (3)

in which R " ^{1 has} the same meaning as the substituent R" of the formula (1) with the exception of the hydrogen atom and in which Z has the same meaning as that given with regard to formula (2) and the further group Z is identical or different,

4) (R ¹¹ O) ₂ POP (OR ' ¹ ^ (4)

6 0

wherein R "has the same meaning as the group R" of the formula (1),

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5) OR "
(R "0) ₂ P-0-P-0-P (0R") ₂ (5)

O O O

wherein R "has the same meaning as R" of the formula (1),

6) OR "OR"

Z-P-O-P-Z (6)

Il ti

0 0

where R "and Z have the same meaning as R" of the formula (1) or Z of the formula (2), the other groups Z being identical or can be different,

7) (R ¹ O) ₃ P (7)

wherein R "has the same meaning as that given for the group R" of the formula (1),

8) Z (R ¹ O) ₂ P (8)

where R "and Z have the same meaning as R" of the formula (1) or Z of the formula (2),

9) Z ₂ (R "'O) P (9)

where R ¹ "and Z have the same meaning as R" ¹ in the formula (j5) and Z in the formula (2) and the other groups Z can be identical or different,

10) (R ¹¹ O) ₂ POP (OR ") ₂ (10)

wherein R "has the same meaning as R" of the formula (1),

11) a halogen-containing phosphorus compound such as a phosphorus oxyhalide or a phosphorus halide or a combination of one of the said halogen-containing phosphorus compounds with water and

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12) a combination of a phosphorus compound such as phosphorus oxide and compounds having phosphorus-halogen bonds, preferably a phosphorus oxyhalide of the formula POX- *, where X is a halogenator means with a compound such as an aliphatic alcohol having 1-12, preferably 2-4, carbon atoms, one aliphatic polyhydric alcohol with 1-12, preferably 2-4, carbon atoms, "epoxides derived from olefins or halogenated Olefins having 2-12 carbon atoms, preferably 3-6 Derive carbon atoms, or dialkyl ethers with 4-8 carbon atoms, preferably 4-6 carbon atoms, provided that when a dialkyl ether is used, phosphorus oxide is used as the phosphorus compound is used, which are the constituents that the esters of oxyacids, of phosphorus or the POC bond as reaction products result,

with the further requirement that if a metallic connection is used as reactant I, a halide or an alkoxy halide is used, and if a plurality of metallic compounds, at least one of which should contain halogen, and if the halogen-containing Phosphorus compound of group (11) of II or a combination of one of these compounds with water is used, an alcoholate of the formula (i) with η = 3 or an alcoholate with η = 4 of the formula (ii) Reactant I is used.

When an alkoxy compound is selected from the aluminum compounds of formula (i) as reactant I, it is preferred a fully esterified product and not a partially esterified product as a phosphorus-containing compound in the reactant II selected.

So far, various catalysts have been used for homopolymerization or copolymerization suggested by vicinal alkylene oxides.

For example, catalyst systems consisting essentially of organic Compounds of the metals of group II or III of the periodic table, e.g. from organoaluminum compounds, organozinc Compounds or organomagnesium compounds

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etc. passed, suggested and some of these are also im Commercially available. These types of catalyst have common technical disadvantages in that they are generally required catalytic amount per unit amount of the monomer is large and that it is dangerous or disadvantageous to handle because they are flammable and quickly lose their catalytic activity in the air. Furthermore, they are essentially Catalysts composed of organozinc compounds are valuable for the polymerization of olefin oxides relatively easier Structures such as ethylene oxide, propylene oxide etc., however, show

in the
they do not have any practical level of useful catalytic activity for the polymerization of halogen-substituted oxides such as epihalohydrins. Thus, their utility is severely limited with respect to the type of vicinal alkylene oxides that can be used.

It has also been suggested the reaction products of aluminum alcoholates with phosphoric or phosphonic acids, probably aluminum phosphate, as a catalyst for the polymerization of vicinal Alkylene oxides (U.S. Patent No. 3,244,646). In comparison with these inorganic salt catalysts, the Catalysts obtained according to the present invention from the specified combinations have far better activities. Respect on the rate of polymerization and the degree of polymerization.

The use of Group IV metal polyphosphates, such as titanium and Zr as a catalyst has been proposed as an example of using the metals of Group IV of the periodic table [CA. 63_, 10071 g - 100726 (1965)], however, these suffer Catalysts again have severe restrictions on the type of vicinal alkylene oxides that can be used, i. these catalysts show only a low polymerization activity for ethylene oxide alone.

Other proposals for using the Group IV metals are known, such as the use of a tin halide diamine complex (East German Patent No. 55431/67), the use of a Tin (II) salt of a carboxylic acid (U.S. Patent No. 2,933,459)

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and the use of the reaction product of stannous chloride with alkylene oxide (U.S. Patent No. 3,248,347). However deliver these catalysts are only polymers with relatively low molecular weights, with regard to the type of to be used Alkylene oxides are limited and must be used in large quantities to give acceptable results.

It is known that so-called Friedel-Crafts catalysts, such as the halides of Al, Zn and Zr, can be used for the polymerization Various alkylene oxides are, but it is also known that they are not able to polymerizate with high To give molecular weight.

It has now surprisingly been found that it is possible to overcome the disadvantages of the known catalysts by the reaction products of the metallic compound or the metallic Compounds selected from the compounds of the formula (i) to (iii) given above as reactants I with the phosphorus-containing compound or compounds, selected from the twelve specified groups as reactants II, the combination of reactants being the specified restrictions on their selection, high catalytic activity for a wide variety of vicinals Show alkylene oxides. They also show a high stability and are therefore easy during their manufacture, storage and to handle their use in the polymerization systems. The catalytic amounts used are compared to the Amounts of conventional catalysts are small, and they give equally satisfactory results at relatively low polymerization temperatures and form vicinal alkylene oxide polymers with Adjustable molecular weights and crystallinities as required, ranging from the amorphous state to the crystalline state -stretch. -Thus, the disadvantages of the usual procedures can be effectively overcome by the catalysts of the invention.

It is therefore the object of the present invention to provide a polymerization or interpolymerization processes of vicinal alkylene

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oxyden to create the number of improvements described above achieved.

Another object of the present invention is to provide a To create a catalyst for the polymerization of vicinal alkylene oxides in the polymerization or copolymerization processes indicated above is useful.

The catalyst of the invention is any of the reaction products which is obtained when at least one of the metallic compounds of the formulas (i) to (iii) is used as a reactant I reacts with at least one of the phosphorus-containing compounds of groups (1) to (12) as reactant II. The reaction product can be used as prepared or purified before use. In most Cases are the reaction products of one or two metallic compounds of I and a phosphorus-containing compound of II used.

When a metallic compound is selected from I, a halide or an alkoxy halide is selected from the compounds of formulas (i) to (iii), and when a plurality of metallic compounds are used, a combination of the compounds of different metals should be selected. In the latter case, at least one of the metal compounds should contain halogen. W Further, when a halogen-containing phosphorus compound is used as a reactant II, is as a reactant I is at least a alkoxides selected from alkoxides of the formula (i) where η = 3 means and the alcoholates of the formula (ii) wherein η = 4, used.

As mentioned before, when a halogenated alkoxy compound, which is represented by the formula (i), i.e. the compound in which R is an alkoxy radical and η is 1 or 2, is selected as reactant I, the phosphorus-containing compound of reactant II is a fully esterified one Product preferred to partially esterified product.

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The catalyst-forming reactants are combined freely as desired, as long as the specified restrictions are observed will. The following combinations can be named as preferred examples:

The reactant I is an aluminum trihalide of the formula (i), wherein η = O, with a compound of Group 1, wherein R "is an alkyl group of 1-12, preferably 2-8, carbon atoms or a halogenated alkyl group of 1-12, preferably 2-4, carbon atoms, used as reactant II.

As reactant I is a tetrahalide of a metal of group IV of the formula (ii), wherein M is Ti, Zr, Hf or Sn and m = O, with a compound of group 1, in which R "is an alkyl group having 1-12, preferably 2-8, carbon atoms and a halogenated alkyl group having 1-2, preferably 2-4, carbon atoms is used as reactant II.

A tin dihalide of the formula (iii) in which X is chlorine or bromine is used as reactant I with a compound of group 1, in which R "is an alkyl group having 1-12, preferably 2-8, carbon atoms and a halogenated alkyl group with 1-12, preferably 2-4, carbon atoms, is used as reactant II.

will
As reactants * Γ ") a combination of compounds of the same metal, such as eihem aluminum trialkoxide of the formula (i), in which R is an alkoxy group having 1-8 carbon atoms and η = 3, and an aluminum trihalide of the formula (i), in which X is Is halogen atom and η = 0, a compound of group 1 is used as reactant II, in which R "denotes an alkyl group with 1-12, preferably 2-8, carbon atoms or a halogenated alkyl group with 1-12, preferably 2-4, carbon atoms, used.

If one uses a combination of compounds as reactant I. various metals, such as an aluminum trial alcoholate

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of formula (i), wherein R is an alkoxy group having 1-8 carbon atoms and η = 5, and a silicon halide, an alkyl or phenyl silicon halide or an alkoxy silicon halide of the formula (ii), in which M is Si and η = 0-2, a compound of the is used as reactant II Group 1, in which R "is an alkyl group having 1-12, preferably 2-8, carbon atoms or a halogenated alkyl group having 1-12, preferably 2-4, carbon atoms.

If a combination of compounds of different metals is used as reactant I, such as an aluminum trial alcoholate of the formula (i), in which R is an alkoxy radical with 1-8 carbon atoms and η = 5, and german! Umhalogenid, alkyl- or phenylgermanium halide or alkoxy- Germanium halide of the formula (ii), in which M is Ge and η = 0-2, a compound of group 1 is used as reactant II in which R "is an alkyl group having 1-12, preferably 2-8, carbon atoms or a halogenated alkyl group with 1-12, preferably 2- k, carbon atoms.

If a combination of compounds of different metals, such as a silicon halide, is used as reactant I, an alkyl or phenyl silicon halide or an alkoxy silicon halide of the formula (ii), in which M is Si and m = 0-2, and a tin halide or an alkyl- or phenyltin halide of the formula (ii), in which M is Sn and m is 0-5, a compound of the formula 1 is used as reactant II, wherein R "represents an alkyl group having 2-8 carbon atoms or a halogenated alkyl group having 2-4 carbon atoms.

In the preferred examples mentioned above, the compounds of formula 1 as reactants II by the combination of group 12, preferably by the combination of Phosphorus oxyhalide of the formula POX ^ (where X is a halogen atom means) with the P-O-C bond-forming component, an aliphatic Alcohol with 1-12, preferably 2-4, carbon atoms can be replaced.

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If further a reaction product of a variety of compounds different metals as reactants I with the Reactant II is used as the catalyst according to the invention, is the addition of an organometallic compound, selected from the following groups (a) to (c), useful as a promoter or accelerator to further increase the catalyst activity to increase:

Organoaluminum compounds of the formula

_p (a)

wherein R ¹ " ^{1 is} an alkyl group with 1-8, preferably 1-4, carbon atoms or the phenyl group, X is a halogen atom, preferably Cl, Br or I, and P is an integer from 1-5;

Organozinc compounds of the formula

Q ₂ Zn (b)

wherein Q is an alkyl radical having 1-4 carbon atoms or the phenyl group means and

organomagnesium compounds of the formula

Q ₂ Mg (c)

wherein Q has the meaning given above.

The preferred range of amounts of the promoter or accelerator is 0.01 to 100 %, preferably 0.1 to 50% by weight , based on the reaction product which serves as the main catalyst. In this case, if the catalyst and the accelerator are mixed or brought into contact beforehand, the catalytic activity may be lowered in certain cases. It is therefore preferred to enter the two materials simultaneously or at different times into the polymerization zone in the presence of the

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adding vicinal alkylene oxide. For example will either the catalyst or the promoter is introduced into the polymerization area and later the other partner becomes either added at the beginning or during the polymerization.

It will be understood that although the above are preferred examples of combinations catalyst-forming reactants are indicated, other combinations can also be used.

The exact compositions or structures of the reaction products the reactants I and II have not yet been clarified. It is usually obtained in the form of a white to pale yellow Solids. For example, if zirconium tetrachloride is used as the reaction component. Participants I and tri-n-butyl phosphate as reactants II in a molar ratio of 1: 2 is converted into n-butyl chloride distilled off from the system, and the remaining solid product shows high activity for polymerization of various vicinal alkylene oxides.

In one example, elemental analysis, the solid reaction product has a carbon content of 28.4 wt -.% And a hydrogen content of 5 ~ 6 wt -.%. The details of the structure of the product are not clear, but from these analytical values alone it was concluded that initially a phosphoric acid ester salt of halogenated zirconium of the formula

^C 4 ^H 9 ° _V I / ^OC 4 ^H 9 PO-Zr-O-P '

C ₄ H _q O II I | l OC ₄ H

^{4 y} ο ei ο ^{4 y}

(calculated value of carbon content: J4.9 %)

which is then condensed into a structure roughly similar to the following structure:

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CHO / 0 Cl 0
PO-Zr-OP-OC ₄ H
Cl I 0 C ₄ H ₉ O Cl C ₄ H 0 0 cl

(calculated value of the carbon content: 27.9 %)

Of course, the present invention is intended by the above proposed Structure should not be restricted in any way. If the reaction continues until the carbon content and the hydrogen content reaches 0, it is found that the catalytic Activity of the reaction product is significantly reduced. Hence, it is necessary to have such an excessive response avoid, and it is necessary to stop this reaction at an appropriate time which can easily be determined empirically. When the organic phosphoric acid ester is replaced by inorganic phosphoric acid or a metal phosphate, this shows Reaction product does not have useful catalytic activity. It is therefore believed that the presence of the structure that passes through the chemical reaction of the ester with an oxy acid of phosphorus the reactant I forms, has an important meaning with regard to the effect according to the invention, but this Statement is again not intended to limit the present invention.

The catalysts according to the invention show a satisfactory one Stability, although in certain cases its catalytic activity can be reduced to a certain extent by prolonged contact with moisture. In particular, they show excellent Storage stability when as solutions in hydrocarbons, especially aromatic hydrocarbons such as benzene, toluene or xylene. They are completely inert to dry air and show no hazards in handling .

Although the reaction of reactants I and II takes place at room temperature in some cases, it is preferably at

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elevated temperatures, eg room temperature until 4OO ° C, preferably 50-400 ° C, at a bevorzugtesten, temperature to 100 300 ⁰ C is performed.

If a variety of compounds of different metals are used as reactants I, the metallic Compounds and the reactants II can be added simultaneously into the reaction zone, or optionally two of the compounds first and then the other compounds are added later. According to a preferred embodiment the metallic compounds are mixed beforehand and the reactant II to be reacted therewith is added to the mixture.

The reaction is usually carried out in the absence of a solvent carried out, however, if desired, inert hydrocarbons, such as heptane, benzene or halogenated hydrocarbons, such as carbon tetrachloride can be used as a solvent. It is also permissible to use a solvent that does Metal halide dissolves, such as an ether. The reaction can be carried out in air, however the reaction is in one. inert gas atmosphere, such as in an atmosphere of nitrogen, Argon, carbon dioxide, etc., are preferred, especially when an easily oxidizable component is used.

In the course of the reaction, by-products that are common to each used special combination of reactants I and II differentiate, such as alkyl halides, aryl halides, alkenes, Alcohols, etc., which are suitably distilled off from the system under the elevated temperature conditions. if If the catalysts are to be produced in large quantities, the reaction is preferably carried out with stirring.

The molar ratio of the reactants is variable over a wide range and is not subject to any particular restrictions. Usually about 0.01-50 moles of reactant II per mole of reactant I (if multiple compounds are used, per mole of total metal compounds used)

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used. Preferably the amount of reactant is II about 0.1-15 moles, more preferably 0.1-10 moles, per mole of the Reactant I. When different compounds are used as reactant I, the molar ratio can be below these connections can be freely selected. For example, if two metallic Compounds are used, a molar ratio of about 1:10 to 10: 1 can also be used.

The reaction products of reactants I and II are so as they are, useful as polymerization catalysts for vicinal Alkylene oxides, but they can if desired under reduced Pressure and / or heating can be cleaned to remove the volatile components, such as the unreacted components and to separate the by-products. They can also be washed with a suitable washing solvent such as hexane, heptane or ether, or by dissolving in a suitable solvent such as benzene, toluene and xylene and reprecipitating therefrom will. In certain cases they can be dissolved in a suitable solvent, e.g. benzene, and for a predetermined time Time can be left under heating or at room temperature, so that they are with an increased or stabilized catalytic activity.

The reaction product can be added to the polymerization system as a solid or as a solution. When used as a solid it is preferably ground before use.

Specific examples of the aluminum compounds of formula (i) among the reactants I include, for example, aluminum halides of formula (i) wherein η = 1, such as AlCl ,, AlBr, and AlJ ^, monoalkyl, monoaryl or monoalkoxy aluminum halides, wherein η = 0 means like CH ^ AlCl ₂ , C ₃ H ₁ -AlBr ₂ , C ₂ Ht-AlCl ₂ , isoC _r H _g AlCl ₂ , C ₆ H ₅ AlJ ₂ , C ₂ H ₅ OAlCl ₂ , C ₃ H ₇ OAlBr ₂ , isoC, H ₇ OAlCl ₂ , ISoC ₅ H ₁₁ OAlJ ₂ , nC ₄ H _g OAlCl ₂ and ISoC ₄ H ₉ OAlBr ₂ ; Dialkyl, diaryl or dialkoxy aluminum monohalides, in which η = 2, such as (C ₂ H ₅ ) ₂ A1C1, (UC ₅ H ₇ ) ₂ A1J, (ISoC ₄ H ₉ ) ₂ AlBr, (C (C ₂ H ₅ O) ₂ AlCl, (ISoC ^ H ₇ O) ₂ AlBr, (n C ₄ H ₉ O) ₂ AlJ and

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and trialkyl, triaryl or trialkoxy aluminum with η = ~ 5, such as (CH ₅ J ₅ Al, (C ₂ H ₅ ) ^ Al, (nC ₅ H ₇ ) ₂ Al, (ISoC ₄ H ₉ ^ Al, (CgH ^ Al, (CH ₅ O) ₅ Al ₅ (C ₂ H ₅ O) ₅ Al, (IsOC ₃ H ₇ O) ₅ Al, CnC ₅ H ₇ O) ₃ Al, CnC ₄ H ₉ O) ₅ Al, (IsOC ₄ H ₉ O) ₅ Al, Ct-C ₄ H ₉ O) ₅ Al, CnC ₅ H ₁₁ O) ₅ Al, CiSoC ₅ H ₁₁ O) ^ Al, CnC ₆ H ₁₅ O) ₅ Al , CnCgH ₁₇ O) ₅ Al and (C ₆ H ₅ CH ₂ O) ₅ Al.

Specific examples of compounds of Group IV metals of formula (ii) as reactants I when M is silicon, silicon _{halides with m = 0, such as SiP 4} , SiCl ₄ , SlBr ₄ and SiJ ₄ , alkyl, aryl or Alkoxysilicon trihalides with m = 1, such as CH, SJCL ₅ , CH ₅ SiBr ₅ , C ₃ H ₅ SiJ ₅ , C ₆ H ₅ SiBr ₅ and C ₂ H ₅ OSiCl ₅ J dialkyl, diary 1 or dialkoxysilicon dihalides with m = 2 such as (CH ₅ ) ^ iCl ₂ , (C ₆ H ₅ ) ^ iBr ₃ , (CH ₂ = CH) ₂ SiCl ₂ , (C ₂ H ₅ O) ₂ SiCl _2, and (C ₅ H ₇ O) ₂ SiJ ₂ ; Trialkyl, triaryl or trialkoxysilicon halides with m = 3, such as (CH _v USiCl, (C ₂ H ₅ U SiBr, (C ₆ H ₅ USiJ, (C ₂ H ₅ O) ₅ SiCl and (C ₅ II O ) ₅ SiBr; tetraalkyl-, tetraaryl-, tetraalkoxy- or alkylallccxysilicon compounds with m = 4, such as (CH ^ ₄ Si, (C ₄ Hg) ₄ Si, (CH ^) ₅ SiCH ₂ CH = CH ₂ , (C ₆ H ₅ ) ₄ Si, (C ₂ H ₅ O) ₄ Si, (C ₅ H ₇ O) Si, (CH ₅ ) ₂ Si (OCH ₅ ) ₂ , C ₆ H ₅ Si (OC ₂ II ₅ ) ₅ and (C ₂ H ₅ ) ₅ SiOC ₂ H ₅ ; if M is germanium, germanium halides with m = O, such as GeF ₄ , GeCl ₄ , GeBr ₄ and GeJ ₄ ; monoalkyl- or monoalkoxy-germanium trihalides with m = 1, Hc- ) CL ,, Ge (CH ^.) Br ^, and Ge (OCH ^) Cl ^; dialkyl or di-

alkoxy-germaniutrdihalides with m = 2, such as ₅₂₂ (C ₆ H ₅ ) ₂ GeBr ₂ , (CH ₅ O) ₂ GeCl ₂ , and (C ₂ H ₅ O) ₂ GeJ ₂ ; Trialkyl geranium

halides, such as (CH--, UGeCl and (CpHf-UGeCl; if M denotes tin, tin halides with m = 0, such as SnF ₄ , SnCl ₄ , SnBr ₄ and SnJ ₄ ; monoalkyl, monoaryl, monoalkenyl or monoaralkyl tin trihalides with m = 1, such as CH ^ SnBr ^, C ₂ Hf-SnCl ₅ , C ₅ H ₇ SnJ, C ₄ HgSnCl ₅ , C ₅ H ₁₁ SnBr ₅ , CgH ₁₇ SnJ ₅ , C ₆ H ₅ SnBr ₅ , C ₆ H ₅ CH ₂ SnCl ₅ and CH ₂ = CHSnCl ₅ ; dialkyl, diary1, dialkenyl or diaralkyltin dihalides with m = 2, such as (CIU) ₂ SnCl ₂
(C ₅ H ₇ ) ₂ SnFp, C ₄ HgSnJ ₃ , (CgH ₁₇ ) ₂ SnCl ₂ ,
and (CH ₂ = CH-CHg) ₂ SnBr ₂ ; Trialkyl, trialkenyl or triaralkyl tin halides with m = 3 »such as (CH ₅ USnJ, (C ₂ H ₅ USnJ, (C ₅ Hg) ₅ SnBr (C ₄ Hg) ₅ SnCl, (CgH ₁₇ ) ₅ SnF, (C ₆ H ₅ ) ₅ SnJ, (C ₆ H ₅ CH ₂ ) ^ nCl and (CH ₂ = CH) ₅ SnBr; tetraalkyl, tetraaryl, tetraalkenyl or

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Tetraaralkyl-tin or alkylalkoxy-tin with m = 4, such as (CpHc) ₄ Sn, (C ₆ H ₅ ) ^ Sn, (CH ₂ = CH) ₄ Sn, (C ₅ H ₅ CHg) ₄ Sn, (C ₅ H ₇ ) gSn (OCH ^) ₂ , (C ₄ H ₉ ) gSniOC ^ gHg,) g and (CgH ₁₇ USn (OC ₄ Hg); if M is titanium, titanium halide with m = O, such as TiCl ₄ , TiBr ₄ , TiJ ₄ etc; monoalkoxy-titanium trihalides with m = 1, such as Ti (OCH ^ ₅ ) Cl ₅ ; Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₃ H ₇ ) Cl ₅ , Ti (OC ₄ H ₉ ) J ₅ and Ti (OCgH ₁₇ ) Cl ₅ ; dialkoxy-titanium dihalides with m = 2, such as Ti (OCgH ₅ ) gClg, Ti (OC ₅ H ₇ ) pBr ₂ , ^T1 (° ^C 6 ^H 13 ^ 2 ^C1 2 ^{and Ti} ( ^OC 7 ^H i5) ^J 2 »trialkoxytitanium halides with m = 5, such as Ti (OCH ₅ ) ₅ Cl, Ti (OCgH ₅ ) ^ r, Ti (OC ₅ H ₇ ) g (OCgH ₅ ) Cl and Ti (QC ₄ Hg) ₅ J; Tetraalkoxy-titanium compounds with m = h, such as Ti (OCH ₅ ) ₄ , Ti (OCgH ₅ ) ₄ , Ti (OC ₅ Hg) ₄ ; and Ti (OCgH ₁₇ ) ₄ ; when M is zirconium , Zirconium halides with m = 0, such as ZrF ₄ , ZrCl ₄ , ZrBr ₄ and ZrJ ₄ ; monoalkoxy-zirconium trihalides with m = · !, such as Zr (OCgH ₅ ) Cl ₅ , Zr (OC ₃ H ₅ ) Br ₅ , Zr ( OC ₅ H) C1 ₅ , Zr (OC ₄ H ₉ ) Br ₅ and Zr (OC gH ₁₅ ) Cl ₅ ; Dialkoxy-zirconium dihalides with m = 2, such as Zr (OC ₃ H ₅ ) ₂ CIg, Zr (OC ₅ H ₇ ) gClg and Zr (OC ₅ H ₁₁ ) Br ₂ ; Trialkoxy-zirconium halides with m = 3 * such as Zr (OCgH ₅ ) -, Br, Zr £ 0C ₅ H ₇ ) ₅ Cl and Zr (OC ₄ Hg) ₅ Cl; and tetraalkoxy zirconium compounds with m = 4, such as Zr (OCHj) ₄ , Zr (OCgH ₅ ) ₄ , Zr (OC ₅ H ₇ ) ₄ , Zr (OC ₄ Hg) ₄ and Zr (OC ₅ H ₁₁ ) J .; and when M is hafnium, hafnium halides with m = 0, such as HfP ₄ , HfCL ₄ , HfBr ₄ and HfJ ₄ ; Monoalkoxy-hafnium trihalides with m = 1 ", such as Hf (OC ₂ H ₅ ) Cl ₅ and Hf (OC ₄ H ₉ ) Br ₅ ; dialkoxy-hafnium dihalides with m = 2, such as Hf (OCgH ₅ ) gCl, Hf (0C ₅ H ₇ ) gBr ₂ and Hf (OC ₅ H ₁₁ ) gJ ₂ ; trialkoxy-hafnium halides with m - 5, such as Hf (OC ₅ Hg) ₅ J and Hf (OC ₄ Hg) ₅ Cl; and tetraalkoxy-hafnium compounds with m = 4, like Hf (OCgH ₅ ) ₄ , Hf (OC ₅ KL) ₄ , Hf (OC ₄ IIg) ₄ and ()

Preferred specific examples of the metallic compounds of the formula (iii) having the reactant I include; and SnBr, ->.

Specific examples of Group 1 of Reactants II include: (CH ₅ J ₅ PO ₄ , (C ₂ H ₅ J ₅ PO ₄ , (C ₅ H ₇ ) ^ O ₄ , (C ₄ Hg) ₅ PO ₄ ,

(C ₅ H ₁₁ ) ₅ po ₄ , (c ₈ H ₁₇ ) ₅ PO ₄ , (cic ₂ h ₄ ) ₅ po ₄ , (ci ₂ c ₅ h ₅ ) ₅ po ₄ ,

(cycloC ₆ H _n ) ₅ PO ₄ , (CHg = CH-CH ₃ ) ^ O ₄ , (BrCgH ₄ ) ₅ PO ₄ , (ClBrC ₅ H ₅ ) - ^

209820/1030

(C ₂ H ₅ ) ₂ HP0 ₄ , (C ₃ H ₇ ) ₂ HPO ₄ , (C ₄ H ₉ ^ HPO ₄ , (CH ₂ = CH CH ₂ ) ₂ P0 ₄ , (Br ₂ C ₃ H ₅ ) ₂ HPO ₄ , (2-C (C ₃ H ₉ ) H ₂ PO _4, and (C ₄ H ₉ ) H ₂ PO ₄ .

Examples of Group 2 compounds of reactant II are as follows: C ₆ H ₅ (C ₂ H ₅ O) ₂ PO, C ₆ H ₅ (C ₄ H ₉ ) ₂ PO, C ₆ H ₅ (C ₈ H ₁₇ O ) ₂ PO, C ₄ H ₉ (C ₄ H ₉ O) ₂ PO, C ₂ H ₅ (C ₃ H ₇ O) ₂ PO, CH ₃ (C ₅ H _n O) ₂ PO, C ₃ H ₇ (C ₂ H ₅ O) ₂ PO, C ₄ H ₉ (C ₂ H ₅ O) ₂ PO, C ₆ H ₅ (C ₂ H ₅ O) HOPO, C ₆ H ₅ (C ₃ H ₇ O) HOPO, C ₄ H ₉ (C ₄ H ₉ O) HOPO and C ₃ H ₇ (C ₂ H ₅ O) HOPO.

Examples of Group 5 compounds include: (C ₆ H ₅ ) ₂ (C ₂ H ₅ O) PO, (C ₆ H ₅ ) ₂ (C ₄ H _{9 O) PO, (C 5} H ₅ ) ₂ (C ₈ H ₁₇ O) PO and (C ₂ H ₅ ) ₂ (C ₂ H ₅ O) P0.

Examples of Group 4 compounds include: (C ₂ H ₅ O) ₂ P-0-P (OC ₂ H ₅ ) ₂ ,

0 0

OH OH
(C ₂ H ₅ O) -POP- (OC ₂ H ₅ ).

0 0

An example of a Group 5 compound is: OC ₂ H ₅ · ;. :

(C ₂ H ₅ 0) ₂ P-0-P-0-P (0C ₂ H ₅ ) ₂ .
0 0 0

Examples of Group 6 compounds include: OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅

0 0 0 0

Examples of Group 7 compounds include: (CH ₃ O) ₃ P, (C ₂ H ₅ O) ₃ P, (C ₃ H ₇ O) ₃ P, (C ₄ H ₉ O) ₃ P, (C ₅ H ₁₁ O) ₃ P, (C ₈ H ₁₇ O) ₃ P, (C ₁₂ H ₂₃ O) ₃ P, (CH ₂ = CHCH ₂ O) ₃ P, (ClC ₂ H ₄ O) P, (C ₂ H ₅ O) ₂ HOP, (C ₃ H ₇ O) ₂ HOP, (C ₄ H ₉ O) ₂ HOP, (CH ₂ = CHCH ₂ O) ₂ HOP, (C ₃ H ₇ O) (HO) ₂ PUnU (C ₁₂ E

Examples of Group 8 compounds include: C ₄ H _g P (OC ₂ H ₅ ) ₂ , CH ₃ P (OC ₂ H ₅ ) _2, and C ₅ H ₅ P (OC ₂ H ₅ ) ₂ ·

209820/1030

Examples of Group 9 compounds include: (C ₆ Iy ₂ P (OCH ₃ ), (C ₆ H ₅ ) ₂ P (OC ₂ H ₅ ), C ₂ H ₅ (C ₆ H ₅ ) P (OC ₂ H ₅ ), (C ₂ H ₅ J ₂ P (OC ₂ H ₅ ), CH ₃ (C ₂ H ₅ ) P (OC ₂ H ₅ ) and (C ₄ Ii ₉ J ₂ P (OC ₂ H ₅ ).

Specific examples of Group 10 compounds include: (C ₂ H ₅ O) _? POP (OC ₂ H ₅ J ₂ , (C ₃ H ₇ O) ₂ POP (OC ₃ Ii ₇ ) ₂ and (C ₄ H ₉ O) ₂ POP (OC ₄ II ₉ J ₂ .

Specific examples of the Group 11 halogen-containing phosphorus compounds associated with the metal alcoholate selected from Alcoholates of the formula (i) of the reactant I, in which η = 5, and the alcoholates of the formula (ii), in which η =

(. be implemented,
meaninget) include, besides phosphorus oxyhalide, phosphorus trihalide represented by the formula PX ^ (in which X is an Ilalogen atom) and phosphorus pentahalide of the formula PXc (in which X is a halogen atom). The phosphorus trihalides, in particular phosphorus trichloride, are preferred.

Among the reactants II, phosphorus compounds to be used in combination with the POC bond-forming constituent of group 12 include, for example, inorganic phosphorus compounds such as phosphorus trioxide, phosphorus tetroxide, phosphorus pentachloride, phosphorus halides, represented by the formulas PX ,, or PXj-, and phosphorus oxyhalides, represented by the formula POX ^ (where X is a halogen atom), as well as compounds of the formulas XD ₂ PO, X ₂ DPO, XD ₃ P and X ₃ DP, where X is a halogen atom and D is an alkyl group having 1-8 carbon atoms, the Phenyl group or an alkoxy group having 2-8 carbon atoms may be mentioned. Specific examples are the following:

(C ₂ H ₅ O) ₂ ClPO, (C ₈ H ₁₇ O) ₂ BrPO, (C ₄ H ₉ J ₂ JPO, (C ₆ H ₅ J ₂ BrPO, (C ₃ H ₇ O) Cl ₂ PO, ( C ₄ H ₉ O) Br ₂ PO, C ₆ H ₅ Cl ₂ PO, (C ₂ H ₅ O) ₂ PCl, (C ₈ H ₁₇ O) ₂ PBr, (C ₄ H ₉ ) ₂ PJ, (C ₆ H ₅ ) ₂ PBr, (C ₅ H ₁₁ O) PBr ₂ , (C ₃ H ₇ O) PCl ₂ , C ₆ H ₁₃ PJ ₂ , C ₆ H ₅ PCl ₂ .

As compounds to be combined with the above phosphorus compounds to form the reaction products

209820/1030

of group 12 can be aliphatic alcohols, such as CH ₃ OH, C ₃ H ₅ OH, C ₅ H ₇ OH, C ₄ H ₉ OH, C ₅ H ₁₁ OH, C ₆ H ₁₃ OH, CyCIoC ₆ H ₁₁ OH , CoH ₁₇ OH, CH ₀ -CH-CH ₀ OH,. CH ₀ -OH and C ₇ H ₁ -OH,

Oil / t d. t d. \ cL \ JD

Cl Cl Cl OH

aliphatic polyhydric alcohols, such as HOCH ₂ CH ₂ OH, HOCH ₂ -CH-OH,

CH ₀ -CH-CH ₀ , CH ₀ -CH-CH ₀ , CH ₀ -CH-CH ₀ , HIGH ₀ -CH ₀ -O-CH ₀ -CH ₀ -CH ₀ Oh

\ cL \\ d \ d. \\ d. \ c. \\ d. <± et d d d.

OH OH OH OH Cl OH OH OH Cl

and HOCH ₂ -Ch-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ OH

and epoxides, which are derived from olefins having 2-12 carbon atoms

derive such as CH ₀ -CH, CH ₀ -CH-CH _x , CH ₀ -CH-CII ₀ -CH _x ,

0 0 0

► CH ₃

CH ₀ -C, CH _x -CH-CH-CH _x , CH ₀ -CH-CH ₀ -CH ₀ -CH ₀ -CH _x ,

\ ' NOH _x \ / \ /

^U *> 0 0

CH ₀ -CH-CH ₀ -Cl and CH ₀ -CH-CH ₀ Br

0 0

to be named.

In addition, dialkyl ethers to be combined with phosphorus oxide can be used Dipropyl ether and dibutyl ether are mentioned.

As a promoter or activator that works simultaneously with the catalyst, which is formed by the reactants I and II can be used v / ground, the following can be named:

(CH ₃ J ₂ AlBr, (C ₂ H ₅ ) ₂ A1C1, (C ₂ H ₅ ),

(C ₆ H ₅ J ₂ AlBr, (C ₆ H ₅ ) ₂ ALJ, CH ₃ AlCl ₂ , CH ₃ AlJ ₂ , C ₂ II ₅ AlCl ₂ , C ₂ H ₅ AlBr ₂ , C ₃ H ₇ AlBr, C ₄ H ₉ AlCl ₂ , C ₄ H ₉ AlBr ₂ , C ₄ H ₉ AlJ ₂ , CgH ₅ AlCl ₂ , C ₆ H ₅ AlBr ₃ .

Examples of organozinc compounds DER formula (b) are t dialkyl zinc compounds, such as. (C ₂ H ₅ JpZnJ, (^ Η, ΟρΖη and (CGH _R) pZn?, And examples of organomagnesium compounds of the formula (c) are dialkylmagnesium -Compounds such as (C ₃ H ₇ I ₀ Mg, (C ₄ H ₇ I ₂ Mg and (C ₆ H ₅ I ₃ Mg ₀

'209820/1030

The catalysts of the present invention are useful in preparation of homo- or copolymers of vicinal alkylene oxides with

a freely selectable molecular weight varying over a wide range and a varying crystallinity, ie from the amorphous to the crystalline state. These variations in molecular weight and crystallinity can be controlled by a suitable selection of the specific reactants I and II Catalyst is used, a polymer of high crystallinity and having a high degree of polymerization is formed. If, on the other hand, SnClg is replaced by a halide of Ti ₄ Zr or Hf in the said catalyst, polymers of medium crystallinity with a high degree of polymerization are obtained. When the SnClp is replaced by a halide of Si, Ge or Sn (tetravalent), the catalyst tends to give polymers having a lower degree of polymerization than in the previous case. With the catalyst in which an aluminum halide is used, amorphous polymers with a relatively low degree of polymerization are obtained. In contrast, the reaction products used as catalysts of a mixture of aluminum halide or alcoholate and SiClj, or GeCl ^ with an ester of a phosphorusoxy acid lead to amorphous polymers with a high degree of polymerization.

Generally speaking, the choice of specific influences Compound or compounds of reactant I. the crystallinity and / or the degree of polymerization of the product polymers, whereas the selection of the phosphorus-containing compounds as reactant II appears to have little effect has the polymer properties. Furthermore, the nature of the organic radicals in the reactants I and II affects the smooth course only the catalyst formation reaction, whereas the nature of the organic residues contained in the reaction product does not have a great effect on crystallinity and / or shows the degree of polymerization of the product polymers. How however already mentioned, possesses the presence of the distinguished from the

203820/1030

chemical reaction of an ester of a, phqsphoroxy acid with a

! ^ derived structure

or more compounds of the formula I) have a very significant effect on the catalytic activity. Therefore, according to the present invention the nature of the organic radicals in reactants I and II over a considerable extent Range variable.

The inventive polymerization of vicinal alkylene oxides is carried out using the new catalysts described above. The polymerization temperature and the amount of the catalyst are not critical, so that normal temperatures not lower than 0 ^° C. and the catalytic amount are used. For example gelegentlieh temperatures in the range of from 0 - 100 ⁰ C and a catalytic amount of 0.1-2 wt .- ^ based on the vicinal AIkylenoxyd monomers (or monomer mixture) used. If desired, it is of course possible to use more than 2 wt -.% Of the stabilizer, based on the monomers to be used, but this is unnecessary. Temperatures can continue, if desired, _s be used to -20 ⁰ C or up to 200 ° C, however, this is not necessary.

The polymerization proceeds equally well in the absence or in the presence of a solvent. As the solvent, any organic solvent may be inert to the _s your catalyst and the monomers, are used. ", With no other critical

ψ table restrictions are in place. For example, aliphatic * alkyl ethers, such as diethyl ether, dipropyl ether, DI-isopropyl ether etc; aromatic hydrocarbons which ete by halogen atoms, lower AltejFlreste may be _o substituted, such as benzene, toluene ,, chlorobenzene etc _e j saturated aliphatlsche hydrocarbon such as propane _s pentane ,, hexane, heptane and higher alkanes% alleycllsche hydrocarbons ^ as C ^ elohexan and methyl be erwsndet C3? clohexanj haloalkanes _s as Methylehlorid, Methyienehlorida chloroform _s carbon tetrachloride and Itia ^ flendlelilor ID _s and mixtures of the above LösungsisälttsI ¥ «.

Bsi the irorllegenäen erflnöungsgemäßeirL IeTfsmj ¹ ^ ^ ssyg · ds ^ Katap a hotie stability auete ®Ιζϊ © aslis- £ 2: u l '/ _s IfcSt

by performing the polymerization and maintaining it a good reproducibility, the reaction is considerably facilitated. In addition, only a small amount of the Catalyst in a satisfactory manner the desired effect, thus the possibly harmful effect of the remaining Catalyst in the polymer on the polymer appearance, e.g. a discoloration, or the "change in the polymer properties s e i t i gt.

In particular, amorphous high polymers of epihalohydrins, which are useful as synthetic rubber, are normally by receive polymerization in bulk or in solution. However, if the polymerization in the presence of the catalyst and aliphatic hydrocarbons as solvents with stirring at a suitable rate can rubbery product can be recovered as a granular precipitate. In such a process, the minor stages are such as the separation of the solvent, etc., is significantly simplified.

The process according to the invention can be carried out either continuously or batchwise.

The present process is based on homo- or interpolymerization a variety of vicinal alkylene oxides applicable. Examples of such vicinal alkylene oxide conomers can be the following are mentioned:

Vieinal alley oxides of the following formula (1)

wherein R ₁ , R ", R _v and R>, (a) hydrogen atoms, (b) saturated or

LdJ H

unsaturated aliphatic hydrocarbon radicals with 1 - 3.8 carbon atoms, vio in the substituents B ^ - Rj ₁ do not form a ring, ic) aryl-substituted radicals of group (b) _a (d) radicals substituted with cycloalkyl radicals with 5-7 carbon atoms

20S820 / 1030

Group (b), (e) halogen-substituted radicals of groups (b), (c) and (d); (f) aryl radicals which are linked to aliphatic radicals with 1-12 May be substituted with carbon atoms or with halogen atoms; (g) saturated or unsaturated cycloalkyl radicals with 5-7 Carbon atoms with aliphatic radicals with 1-12 carbon atoms and / or halogen atoms can be substituted; (h) residues of groups (b) to (g) which contain epoxy groups; (i) residues of the following formula (2)

-R'-O-R "(2) and

(j) residues of the formula

Il

-R'-O-C-R "(j5), mean,

wherein in the formulas (2) and (3) R ¹ -CH ₂ - and R "represents a member of the following group:

(i) saturated or unsaturated aliphatic radicals with 1-18 Carbon atoms;

(ii) the radicals mentioned under (i) which are substituted by aryl groups are;

(iii) the radicals of group (i) with cycloalkyl groups with 5-7 carbon atoms are substituted;

(iv) Aryl residues, which may contain side chains with 1 - 1? Carbon atoms contain;

(V) Cycloalkyl radicals, which optionally have side chains with 1-12

Contain carbon atoms; and (vi) halogen-substituted radicals of groups (i) to (v).

Specific examples of such many alkylene oxides are: olefin oxides, i ο ethylene oxide, propylene; xyd, 1-butene oxide, 2-butene oxide, isobutene oxide, 1-hexene oxide, 1-octene oxide, butylene monoxide, cyclohexone oxide and vinyl cyclohexene monoxide; aromatically substituted olefin oxide, vne styrene oxide, oC-methyl styrene oxide, ß-methyl styrene oxide, ρ-methyl styrene oxide, p-chlorostyrene oxide, o-chlorate styrene oxide and glycidyl benzene; halopenated O] ofinoxides, such as Epichlorliydj'jn, J π l; i orr.hydrin, Epi iodhydrin, EjI ■ \ c ^ rhydrln, 2-Hethyl-

209820/1030

ÖWGINAL

epichlorohydrin, jJjJijS-trichloropropylene oxide and 4,4,4-trichloro-1-butene oxide; Glycidyl ethers, such as methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, cyclohexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, p-chlorophenyl glycidyl ether and allyl glycidyl ether; Glycidyl esters of monocarboxylic acids such as glycidyl acetate, glycidyl propionate, glycidyl monochloroacetate, glycidyl benzoate, glycidyl acrylate, glycidyl methacrylate and glycidyl cyclohexane carboxylate; Diepoxides of diolefins such as butadiene dioxide, vinylcyclohexene dioxide and glycidylsilane glycidyl esters of dicarboxylic acids such as glycidyl phthalate, glycidyl maleate and glycidyl succinate ; and diglycidyl ethers, which are the reaction product of bisphenols with epichlorohydrin.

The present invention is to be explained further by means of the following examples.

example 1

In the following Table 1 are examples of the catalyst preparation given from various combinations of reactants I and II. The way of making the catalyst was that the following: a glass reactor with a capacity of 500 ml, equipped with a distillation column, stirrer, heater, and thermometer, was with the reactants I and II, and. if necessary, loaded with a solvent. The system was heated with stirring, whereby the volatile by-products of the reaction were distilled off so that the reaction system was semi-solidified or solidified. The product was subjected to one of the following three post treatments and used as a polymerization catalyst used for vicinal alkylene oxide.

(1) The reaction product was allowed to cool in air, pulverized and dried for 2 hours under reduced pressure at room temperature.

209820/1030

(2) The reaction product was allowed to cool in air, washed it twice with hexane and dried it under reduced pressure at 100 ° C. for 2 hours.

The reaction product was allowed to cool in nitrogen gas, washed twice with hexane and dissolved
in benzene.

In Table 1, the "response time" means the heating time the highest reaction temperature. If necessary, the reactions and post-treatment were carried out in nitrogen gas,

209820/1030

■> * · rs Respondent I. verv / eniote
K-ir.ro (:) Table 1 solvent
Kind of amount
(ml) Highest React To Bemer i ^r ? or ~ c ". ? 6.6 Reaction participants II Ethyl 50
ether Reaction
temp.
(° c) functional
(Min.) treat
lung kungen 2 AiCl ₅ 41.0 used
Formula! '! Narrow (β) - 135 15th (D in N ₂ -
gas AU ₃ 26.7 (HC ₂₁ HqO) ₃ PO 108.0 - 120 15th (2) do. σ
co AiBr ^ 25.0 (C ₃ H ₅ O) ₃ P '26.5 n-hexane 30 140 10 (2) OO
C. CH- AlCi- 35.8 ^ ¹¹ C ⁸ H ₁₇ O) ₃ PO 85.0 n-hexane 40 220 15th (2) in Np-
gas ■ »».
«J C -H ^ AiBr ^ 28.6 (C ₂ H ₅ O) ₄ P ₂ O ₃ 58.0 - 185 15th (3) do. 'Cii- OAlCi- 55.0 - 175 15th (2) W. TiJ ₄ 'IBr ₂ 62.0 (nC ₄ HO) ₂ PO (OH) 21.0 - 205 10 (2) in Np-
gas (IC ₃ H ₇ C) ₂ T. . 23.3 (C ₂ H ₅ O) ₃ PO 66.5 - 140 10 (2) ZrCl ₂ , <■ -.? O (C ₂ H ₅ ) (IiC ₅ H ₇ O) ₂ PO 35.0 185 10 (2) rs; (HC ₄ H ₉ O) ₅ PO 54.0 170 10 (2) 120370 P ₂ O ₅ 27.5
nC ₄ H _q 0H 40.0

1 m Q

170 10 (1) in No.
Gas * 160 ' 10 (2) 195 15th (2)

Table l (continued)

11 ZrBr ₄ 23 3 FCCl 30.0

nC ₄ H ₉ OH 40.0

12 HfCl ₄ 33.0 UC ₄ Ii ₉ O) ₃ PO 54.0

13 CnC ₄ II ₉ C) ₂ ZrCl ₂ 31.0 CgH ₅ (CgH ₁₇ O) ₂ PO 47.0

14 KfCl ₄ ; . 33.0 PBr ₃ 22.0

CH ₂ = CHCH ₂ OH 80.0

15 SiCl ₄ 34.0 (CH ₂ = CHCH ₂ O) ₃ PO IO5.O - 170 20 (2)

ro -, ■

216 UeCl ₄ 42.5 (ClCH ₂ -CH ₂ CH ₂ O) ₃ PO 78.0 - 190 20 (2)

00.

S ^{17 SnC1} 4 ²⁶ * ° CnC ₄ H ₉ O) ₃ PO 55.0 - 2! 0 10 (2) in N.- *>. "Gas ^c '

^ 18 SnBr ₄ 31.5 (ClCH ₂ CH ₂ O) ₃ PO 135.0 - 205 10 (1) dp

Ca)

° 19 SnCl ₂ 3Ö.0 CnC ₄ II ₉ O) ₃ FO 60.0 240-15 (2)

20 ^SnBr ₂ 25.O CnC ₄ H ₉ O) ₃ PO 78.0 - 250 15 (2)

O 21 GnCl- 33.0 PCBr, 57.0.

Z ^{2 5} 240 15 (2) in N. -

> 1C ₃ H ₇ CH 60.0 _gas 2

S. ■ κι

Sg ^ Al (OiC ₅ H ₇ ) ₃ , 42.0 PCl ₃ 14.0 η-heptane 50, 70 5 (1)

N>

ΓΪ | Z5 Ti (OnC ₄ Ho) ₄ 70.0 POCl, 31.0 - 100 30 (2) S '

Table 1 (continued)

ο 30

31

32

33

24
. 25th

26th
27
> 28 AlCl

Ti ^ OiC ₃ K ₇ )

SiCl,

Alles

CH ₃ SiCl,
3

A1 (OQ ₂ K ₅ ) ₃
^L 4

55.0 PBr ₇

25.0

21.0 ^iViC1 3

42.0

32.6 ^K3r 3

44.0 «p

17.0 17.0

13-3 32.5

41.0 15.2

35.0 36.0

(HC ₃ H ₇ O) ₃ PO

ChC ₃ H ₇ O) ₃ PO

22.0-n-hexane 50 150

31.0 η-hexane

175

15.3 n-hexane 40 140

η-hexane '

160

230

160

n-Hexari '40 185

175

10

15th

10

73.0 ethyl ether 40 135 10

30th

10

10

10

20th

U)

(2) in N ₂ - * £ Gas ⁴ ^

(2)

(2) in gas

(2)

(3) in Nj, -Gas ^

Table 1 (continued)

41
42

"7 τ · ^η 1

EfCl ₁

Y?

^J Z ^r * T ^J ? ^ ^JJ * Z

SiCl,

ZrCl ₁₊

22.8 23.5

23.5

I3.O

48.7

20.4 13.0

25.0 66.0

25.0 12.0

24.0 32.0

22.8

34.0

27.0

58.0 < ^nC 6 ^H 13 ^O) 3 ^P

(nC, H ₉ O) - ^ P

93.0 n-keptane 40 190

35.2 - 210

48.5 ethyl ether 40 145

Carbon tetrachloride 70

₉ O) PO 30.0

54.Ο n-hexane

20th

105.0 η-H ept at 50

54.0 η-hexane
22.0 η-hexane

20th

₂₀₅

.210

190

180

145

10

10

20th

15th

170

10

10

10

20th

(2)

(2)

(2)

C2)

(D

(3) in gas

(2)

OJ

is ° J.

ω. · £; ■ ί

ß cö w

• HO C 'ω

OJ OJ OJ OJ

O OOOOQOiAO

H HHHHHHHH

O IAIAOIAIAIAOO VD IA J ΓΑ H IA IA CO ΓΑ H HOJOJOJOJHHH

O O O O O O • • • • • « J- O IA IA O ^! -A J- CT \ H

OO O O O O

IA O cO H H IA

J-VC O co co co

tA

O"

SO O OJ Q O

& R a fti a «

O CTv CT \ (T \ O ON O O ^ O OP3 O O O W O KN ΓΑ Ο O "j" O OJ C! Ö Ö O -HHOÖ OJ O

^ t ₁ O «- r

O
C. tA O tA υ O
• Η κ>
H
ft. ν ΓΑ
O O O O oj ON IA O O tA O O O O
tA CO
OJ si OJ σ \ η
H OJ tA
OJ OJ
OJ

S ΙΛ Λ O KN IA O Λ tAO tAO OfA OO OO OO

- * O ^- ^ OJ Ν "\ tA H CO IN OJ CT \ IA H CJN H IA OJ KN OC ^ -IA

M HrH C \: OJ OJOJ fA KNOJ HOJ OJOJ N- \ tA OJH

ο J-J-J- J- J- OJ H j- OJ OJ OJ j- J ^ OJ KN J- i-i r-i t-i H H U O H H H H O O O O O m ο PQ O ti -H υ FQ PQ £ -4 Φ OJ ^ O Ö • Η tQ Vi • Η H ■ Η H tQ K C * 3 ΓΑ 0'Y Wi CO Vl Vi
OJ JLfN ON ^ U
SV OJ y- YES ^ ¹ OJ iA J- "ΟΛ O OJ O J- 53 U O * "νθ M O O VD Ρ3 J- «Μ O j α O O) O ν- 'O α CO iQ ^^ χ> α

IA VO C ^ CO Ο> O H

J "J-J-J" J-IA IA

209820/1030

Table 1 (continued)

SiCl.

214O POCl ₃ 15.0 iC, H "C

16.5

10

(2) in Νρ gas

53 Ti (OnC ^ H ₉ )

13.0

32.0

13.0

26.6 η-hexane

38.0

10

(2)

(2)

Example 2

The results of the polymerization of epichlorohydrin using the catalysts prepared in Example 1 are shown in Table 2. The polymerization was carried out as follows.

A tubular polymerization vessel made of glass having a capacity of 100 ml was charged with the catalyst, and the inner atmosphere of the vessel was replaced with nitrogen. Epichlorohydrin, which has been dehydrated to a water content of not more than 20 ppm and, if necessary, a solvent, which has also been dehydrated to a water content of not more than 20 ppm, was then added to the vessel, and the vessel was sealed. The contents were mixed by means of a shaker, and the polymerization was carried out at the indicated temperature. If an alkylated compound of Zn, Mg or Al was added as a promoter, the organometallic compound, diluted in n-heptane, was poured into the vessel immediately after charging with epichlorohydrin. The polymer obtained was dissolved once in hot benzene or hot monochlorobenzene containing 0.5 % Nocrac NS-6 (2,2 * -methylene bis - ^ - methyl-o-tert.buty! Phenol), and the ' Solution was poured into a large excess of methanol. The precipitate thus formed was separated and dried under reduced pressure. In the table, the reduced viscosity is that measured at 80 C in a monochlorobenzene solution with a concentration of 0.1 g / 100 ml. The crystallinity was determined by X-ray diffraction.

209820 / t030

1 catalyst lot
. (s) Table 2 • Art Amount of formula ^J
(G) 20th - 20th - 20th ·. - ⁴ (g? ^{E tetn} p * Re ak-
4- A r \ Y \ et _ AUo -
prey nt amorphous -4 2 No, 0.2 - ; 20th - 40 uxons—
Time
(Hours.) 70 te Visko- Bemer-
sitat kungen do 3 1 0.2 Monomeric solvent accelerator i., "" - - 40 24 38 0.38 do 4th 2 0.2 lot
(G) benzene 40 Zk 50 0.29 do At
sentence
No. 5
6th ι,
T 0.15 40 - 40 Zk 72 0.90 7th 5 0.15
0.15 40 ; 55
55 Zk 50
92 0.75 N)
* δ
9 7th
9 0.1 15th benzene 55 Zk
Zk . 71 1.15
2.05 memfm
ro
σ 10 9 0.1
0.1 40 benzene 60
60 24 75
94 2.20 370 11 10
11 o.o8 S S 55 24
24 77 1.80
1.95 20982 12th 12th 0.1 20th - 55 24 45 1.90 ο 13th 14th 0.2 15th
40 - 45 24 23 1.52 1030 14th 15th 0.2 40 Hexane 30th 48 66 0.14 semi-crystalline
do 15th 17th 0.2 40 - 30th 24 72 .0.70 do 18th 0.15 40 - 40 24 90 0.65 ' do
do 19th 15th 24 1.42 do 40 do 40 do do do crystalline

Table 2 (continued) 1 * 6 20 0.15 kO

2k

17th 21st 0 .2 15th Tetrachlor
carbon benzene 18th 22nd 0 .2 ko - benzene 19th 23 0 .1 ko - benzene 20th 25th 0 .1 ko - benzene 21
IO 26th 0, .2 ko - P. 22 28 0, .2 ko co
«Ο 23
ο 29 0, .2 ko - ^ 24 29 0, .2 ko - ο *> 25
ο 29 0. .2 15th n-hexane 26th 30th 0. , 2 ko - 27 32 0. , 2 ko - 28 33 ' 0. , 08 ko - 29 33 0. 05 10 30th 33 0. 05 10 31 33 0. 05 10 32 33 0. 08 10

33

1.05 crystalline

■ a AlEt, AlEt,
MeEt ₂ 0 ko 2k 70 1 .15 do do i?
<* \ - ZnE tp AKIC ₃ II ₇ ) ₃ 0 ko 2k 65 0 .88 amorphous semi-crystalline - - 60 2k 83 1 .18 . semi-crystalline amorphous - tm 40 2k 89 1 Λ5 amorphous do - - 30th 2k 15th 0 .96 do do - - ko 2k 65 1, .82 do do
do ro 0.
0. -p- -p-
O O 2k
2k '62
89 1,
1. AO
.75 do
do do 12037 20th 0. ko 2k 75 1. .60 0 15th kt 52 1, , 10 ko 2k 78 1. AO 50 2k ■ 82 1. .58 30th 60 2k 78 1. 53 30th
30th 60
60 2k
2k 96
88 3.
2. 55
20th 3.0 30th k8 93 2. 80 .02 .01 ■ .01
, 01 .02

33 » Tabel 0 2 (Continuation - ■ 30th 34 34 0 .2 40 benzene 55 ; 4 0 .2 40 - 36 35 0 .2 10 Tetrachlor benzene 20th 37 36 0, .1 40 carbon benzene 37 .2 15th benzene _ Κ? 33 0, ■ - O 39 .2 40 - CO 39 0. 00
ro 39 .2 40 - CD 40 0. __ » 41 41 0. .2 40 CD
CO 42 , 2 40 - O 42 0, 43 43 0, , 2 40 44 45 0. , 2 40 20th 46 ,1 40 20th O 45 0. 20th I. 46 46 0. 1 20th > 47 46 0. 1 20th NSPi 48 1 20th HI
O 48 0. Uf 49 2 40 O

AlBt,

ZnEt.

AlEt,

AlEt.

0.01

0.02

0.01

0.01

35 24 55 1 .55 amorphous 55 24 87 1 .95 do 45 24 72 1 .40 do 55 24 92 1 .58 semi-crystalline 50 24 53 1 .22 do 40 24 80 1 .55 amorphous 40 24 89 1 .75 do 55 24 95 2, .10 • semi-crystalline «Ν 40 24 70 1, .28 amorphous 45 24 & 5 1. .95 semi-crystalline 25th 24 65 1. , 35 crystalline 25th 24 75 1. ■ 39 do 25th 24 60 1. , 40 do 25th 24 88 1. ■ 85 do ISJ 25th 24 73 1. 58 do _o 55 24 72 1. 28 amorphous ■ * «&

Table 2 (continued)

49 50 0.1 40 50 51 0.2 40 51 52 Ό.Ι 20th 52 53 0.2 40 2098 53 54 0.1 40

MgEt.

benzene

0.01

55 2k 96 2Λ5 semi-crystalline ko Zk 85 1.83 ■ 'amorphous 45 2k 59 1Λ8 do 55 88 1.35 semi-crystalline

2k

k2

1.85

do

ro ο co

Example 3

The results of the polymerization of propylene oxide using the catalysts prepared in Example 1 are given in Table J5. The polymerization procedure was generally similar to that used in Example 2. Propylene oxide, dehydrated to a water content of not more than 15 ppm, was used as the monomer. The resulting polymer was once in about 100 ml of hot acetone containing 0.5 %
Nocrac NS-6 was dissolved, poured into water and the precipitate formed was dried under reduced pressure.
The reduced viscosity was measured in a benzene solution at a concentration of 0.1 g / 100 ml at 40 ° C.

209820/1030

Tabel

approach

Catalyst Monomer Solvent Accelerator _M Quantity Quantity _Type Quantity

^No '. (g) (S) (S)

1 1 0.15 30th 2 3 0.15 30th 3 6th 0.15 15th 4th 8th 0.15 30th O
CO 5 9 0.15 15th OO 6th 10 0.15 ■ 15th 7th 13th 0.10 .15 ό
Approx 8th 16 0.10 15th O 9 17th 0.15 15th 10 19th 0.05 30th 11 24 0.05 30th 12th 27 0.05 15th 13th 29 0.05 15th

benzene

benzene
benzene

benzene

benzene
benzene

15th

It 15

15th

15 15

Formula Rea-

tion reduction

time loot visco-Bemer-

(Std.) {%): Sity kungen

25th 20th 58 3.95 amorphous ro 25th 20th 51 1.80 do 20_3y
• 4 25th 20th 45 2.65 do O 25th 20th 31 1.50 do 40 20th 99 4.95 do 40 20th 86 4.10 do 25th 20th 72 3.30 do 25th 20th 18th 0.95 25th 20th 85 1.58 20th 24 . 92 6.05 25th 20th 32 3-18. .25 20th 75 3.50 25th 20th 65 3.83 semi-crystalline do do amorphous do do

Table 3 (continued)

0.05

31 0.1

16

oo 18

^ 19

^σ 20 co

22nd

0.05

0.05

0.10

0.1

kk 0.1

k6 0.1

k6 0.1

k7 0.15
2k k7 0.15

52 0.1

15 15

15 15 15

30 '30

30 15

30 30

30th

Benzene benzene

Benzene benzene benzene

benzene

15th

15th

15 15

15th

AlEt,

15th

• ÄlEt,

K ₃ et.

ZnEt.

AlEt,

0.01 25th 20th 88 5.91 amorphous 0.01 ■ 25 20th Tj 3.10 do 25th 20th 61 5Λ5 do 0.0 ^ + 25th 20th 96 9.30 do 0.01 20th 20th 89 7.SO do 25th 20th 72 3.85 do 25th 20th 78 5.00 do 25th 20th 85 6Λ0 semi-crystalline D.03 10 ^ 8 82 7.20 do 30th 20th 32 2.85 do D.01 30th 20th 75 3.95 do

30th

20th

60

3.52

amorphous

- ro

Example 4

The results of the polymerization of various epoxides using the catalysts prepared in Example 1 are summarized in Table 4. The polymerization procedure used was generally similar to that used in Example 2. Ethylene oxide was distilled through a column filled with potassium hydroxide prior to polymerization and other epoxides were dehydrated to a water content of not more than 20 ppm. Among the resulting polymers, the "SO" (styrene oxide) and PGE (phenylglycldyl ether) polymers with ethyl ether containing 0.5% Nocrac NS-6 were dried under reduced pressure, and the BO (1-butene oxide) ), BGE (butylglycidyl ether) and AGE (allyl glycidyl ether-JPolymers were washed with methanol or water containing methanol and dried under reduced pressure. Furthermore, the EO (ethylene oxide) polymer was filtered, in ethyl ether containing 0.1 % Nocrac NS-6, immersed and dried under reduced pressure as it was, The viscosity of EO, BO, AGE and BGE polymers was determined in the form of their benzene solutions at a concentration of 0.1 g / 100 ml at 50 ° C and that of the SO and PGE polymers in the form of their monochlorobenzene solutions at a concentration of 0.1 g / 100 ml at 8 ° C.

209820/1030

approach
Mr.

1
2

5
6th

7th
8th

9
10
11
12th

15th

14th

Table Catalyst Monomer Solvent No.

Art

Art

(s)

9 0.08 EO 4

19 0.08 EO 4

46 0.08 EO 4

19 0.10 BO 40

35 0.05 BO 40

50 0.05 BO 40

12 0.20 SO 40

55 0.20 SO 40

9 Ό.10 PGE 40

12 0.05 PGE 40

35 0.05 PGE 40

35 0.15 AGE 40

50 0.15 AGE 40

46 0.10 BGE 40

Hexane hexane

Hexane

5β

Re ak-
functional
temp. Reak
ions
Time
(Hours.) the end
prey
(*) reduce
te visco
sity , 2 ' Bemer
kungen 35 20th 89 7th .8th crystalline 25th 20th 88 8th .6 do 25th 20th 100 12th .8th do 25th 18th 72 4th .5 amorphous 50 18th 85 6th .9 do 50 18th 92 7th .8th do 40 24 25th 0 .8th semi-crystalline 40 24 71 1 , 4 do 50 24 85 1 .9 do 30th 24 42 O .1 do 50 24 95 5 .5 do 30th 24 28 0 .1 amorphous 30th 24 15 · 0 • 5 'do 50 24 86 1 do

KJ O CO -J O

Example 5

The results of the copolymerization of various epoxides using the catalysts prepared in Example 1 are summarized in Table 5. Of the monomers subjected to copolymerization, ethylene oxide was distilled through a column filled with potassium hydroxide, while the other monomers were dehydrated to a water content of not more than 15 ppm. The monomers to be blended-polymerized in each batch were mixed before they were introduced into the polymerization tube. The other polymerization conditions are generally similar to those used in Example 2. The polymerization products of the batches Nos. 3 to 3 were each dissolved in about 100 ml of acetone containing 0.1% Nocrac NS-6, as they were, and dried under reduced pressure. The products of Runs Nos. 4-10 were dissolved in hot acetone containing 0.5 % Nocrac NS-6, poured into a large excess of methanol, and the precipitate thus formed was dried under reduced pressure. The reduced viscosities of the products of batches 1-3 were in the form of their benzene solutions at a concentration of 0.1 g / 100 ml at 50 ° C and those of the remaining products with monochlorobenzene solutions at a concentration of 0.1 g / 100 ml at 80 ° C measured.

All of the polymers obtained in batches No. 1 to 10 were amorphous and had excellent rubber elasticity. With the help of the titration of the iodine value, the allyl glycidyl ether content of the polymer of batch no. 1 was determined to be 8.6 %, the polymer of batch no. 2 to be 7.0% and that of the polymer of the batch No. 3 determined with a value of 7.3 % . The elemental analysis shows that the chlorine contents of the polymers were as follows:

209820/1030

Polymer of batch No. 4 26.5 %,

Polymer of batch no.5 22.6 %,

Polymer of batch no.6 24.0 %,

Polymer of batch no.7 27 * 0 %,

Polymer of batch no.8 7 * 4 %,

Polymer of batch No. 9 34.6 %,

Polymer of batch No. 10 18.3 %

The yield is as weight -% of the polymer expressed to the total weight of the introduced monomers..

209820/1030

approach

Tabel

Catalyst Monomer Solvent Accelerator No. ¹ ^ se _type amount _type amount _pomel amount

0.1

2 19th 0.1 3 33 0.1 20981 4th 19th 0.1 ο 5 33 0.2 1030 6th 46 0.08 7th 33 0.1 δ 33 0.2

52 0.05

46 0.08

PO
AGE 36
4th FO
AGE 37
3 PO
AGZ 18th
1.5 EO
EPCH 6th
34 SO
SPCH 6th
34 EO
SPCH 3
17th PO
EPCH
PO
EPCH 10
30th
32
8th EPCH
AGE 35
5 EO
PO
EPCH 3
7th
30th

benzene

benzene

20th

AlEt

Reaction temp. (- ⁰ C).

30 30 40 20 30 15

50 50

60 25

React

tion reduction

time loot visco-Bemer-

(Std.) {%) Sity kungen

62

80

24 94 10 23 16 18th 12th 22nd 24 8th, 24 96 24 88

3.8 amorphous 5.2 do

9/4 ^do 1/8

13th

28

2.4 3.0

3.5
4.3

1.3
3.7

do do do ^;

do do

do do

Example 6

Epichlorohydrin was in a polymerization vessel with a Fit of 20 1 made of stainless steel (SUS-27) and equipped with a stirrer, thermometer and was provided with a jacket, polymerized.

First, the atmosphere in the vessel was replaced with nitrogen, and then the vessel was charged with a liquid mixture of 3 kg of epichlorohydrin and 12 kg of benzene which had been dehydrated to a water content of not more than 10 ppm. Catalyst No. 33 prepared in Example 1 was added to the system in the form of 50 ml of a benzene solution (concentration 0.3 g / l ml). The amount of the catalyst in this case was 0.10 wt. -%, based on the liquid mixture. Then 2 ml of diethylaluminum were added and the system was polymerized at 60 ° C. for 24 hours. To the resulting extremely viscous polymerization liquid was added 30 g of Nocrac NS-6, and the system was poured into a large excess of methanol. The precipitate thus formed was dried at 50 ° C. to obtain 2.5 kg of epichlorohydrin rubber. This crude rubber had a reduced viscosity of 3 * 05 (80 ° C., 0.1 g / 100 ml monochlorobenzene) and a Mooney viscosity (ML-, u 10O ⁰ C) of 71. The ash content was 0.45 ^. When examined using X-ray diffraction and a differential scanning calorimeter, no crystallinity could be observed.

The raw rubber became a mixture of the following composition processed and the physical properties of the vulcanized product were examined.

209820/103 0

Mix composition: Weight 5 parts component 100 Epichlorohydrin polymer 5.0 Triblei-tetroxyd (red lead) 1.0 Zinc stearate 1.5 2-mereaptoimidazoline 1.0 Nickel dibutyl dithiocarbamate 50 PEF carbon black

Vulcanization:

160 ° C 30 minutes
Physical Properties:

Tensile strength 151 kg / cm ²

Elongation 410 %

200 % module 121 kg / cm ²

Tear strength 57 kg / cm permanent elongation 4 % rebound resilience 29 %.

Aging test (gear system, 96 hours at 150 ^° C) change in tensile strength + 5.9 #

Elongation change - 34.2 % oil resistance test (JIS No. 1 oil, 40 ° C χ 24 hours)

Volume change + 0.5

Weight change + 0.3 oil resistance test (isooctane 70 + toluene

30, 40 ° C χ 24 hours)

Volume change + 18.8 % weight change + 9 * 3 #

209820/1030

Example 7

Example 6 was repeated with the exception that the 12 kg of benzene used there as the polymerization solvent through 11 kg of η-hexane were replaced. With this approach one obtained the polymer in the form of a granular precipitate, the did not adhere to the inner walls of the polymerization vessel. The polymer was separated by filtration, with a Ethyl ether solution containing 20 g of Nocrac NS-6 replaced and, as it was, dried at 50 ° C one an epichlorohydrin rubber: via a relatively simple one Aftercare »

203820/1030

Claims (1)

Patent claims -χ.) Process for polymerizing or copolymerizing vicinal alkylene oxides in the presence of a catalyst to form the corresponding homopolymers or copolymers, characterized in that the reaction is carried out in the presence of the reaction product of the reaction participants I and II listed below as catalysts, ie in Presence of the reaction product of at least one of the following reactants I of the formulas (i) to (iii): (I) Aluminum ^{compounds of the formula R} n A1X 5-n W in which R is an alkyl, alkoxy or aryl radical, X is a halogen atom and η is an integer from 0 to j5; Group IV metal compounds of the formula R 'MXj, (ii) m 4-m ^x ' wherein M is a metal of Group IV of the Periodic Table with atomic numbers from 14-72 and wherein, when M is a Group IVa metal, R 'is an alkyl, alkenyl, • alkoxy, aryl or aralkyl group and wherein when M is a Group IVb metal is, R 'is an alkoxy group, X is a halogen atom and m is an integer from 0-4 mean; and Tin dihalides of the formula SnX ₂ (iii) where X is a halogen atom, with at least one of the reactants II, which is composed of the phosphorus-containing compounds of the following 12 groups is: 209820/1030 (II) (1) (R "O) where R "is hydrogen, an alkyl group with 1-12 carbon atoms, a halogenated alkyl group with 1-12 carbon atoms, an alkenyl group with 1-12 carbon atoms or a cycloalkyl group with 5-7 carbon atoms, the alkyl or alkenyl side chains with 1 -4 carbon atoms, means in which at least one of the groups R "is an organic radical of the above group and the other groups B ^{M can} optionally be identical or different; (2) Z (R ¹¹ O) ₂ PO (2) where R "has the meaning given for the formula (1) and Z is an alkyl radical having 1-8 carbon atoms or is an aryl group; (3) "_; Z ₂ (R" ¹ O) PO (?) where R " ^f has the meaning given in the formula (1) with the exception of hydrogen and Z has the same meaning as the group Z of the formula (2), it being possible for the further groups Z to be identical or different; (R "O) _p POP (OR ^K ) _p (4) 0 0 where R "has the same meaning as the group R "of the formula (1); OR » (R ¹¹ O) ₀ POPOP (OR ⁰ ) _o (5) an ir ft C. 0 0 0 * wherein R "has the same meaning as the group R" of the formula (1); 209820/1030 OR "OR" (6) Z-P-O-P-Z (6) Il Il O O wherein R "and Z have the same meaning as the group R" of the formula (1) or the group Z of the formula (2), in which the further groups Z can optionally be identical or different; (7) (R ¹¹ O) ₃ P (7) wherein R "has the same meaning as R" of the formula (1); (8) Z (R ¹¹ O) ₂ P (8) in which R "and Z have the same meanings as R" of the formula (1) and Z of the formula (2); (9) Z ₂ (R ¹ "O) P (9) in which R " ¹ and Z have the same meanings as the group R ¹¹¹ in the formula (3) or the group Z in the formula (2), where the other groups Z can optionally be identical or different; (10) (R ¹¹ O) ₂ POP (OR ") ₂ (10) wherein R "has the same meaning as the group R ^H in the formula (1); (11) halogen-containing phosphorus compounds such as phosphorus oxyhalides or phosphorus halides, or a combination of the above-mentioned halogen-containing phosphorus compounds with water; and (12) a combination of a phosphorus compound such as phosphorus oxide and compounds having a phosphorus halogen bond with an aliphatic alcohol of 1-12 Carbon atoms, an aliphatic polyvalent Alcohol with 1-12 carbon atoms, epoxies derived from olefins with 2-12 carbon atoms, 209820/1030 or dialkyl ethers having 4-8 carbon atoms, provided that when the dialkyl ether is used, phosphorus oxide as Phosphorus compound is used, which are the constituents that are the esters of the oxyacid of phosphorus or the Form P-O-C bonds as reaction products, provided that when a metal compound is used as reactant I, a halide or a halogenated one Alkoxy compound is used and when several metal compounds be used, at least one of the metal compounds should contain halogen; and when a halogen-containing phosphorus compound of group (11) of reactant II is used in a combination of one of these compounds with water, one or more alcoholates of the formula (i) in which η = 5, or of the formula (ii), in which η = 4, as reactant I be used. d.) Process according to claim 1, characterized in that the reactant I is at least one compound selected from the following group: Aluminum compounds of the formula wherein R is an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkenyl group with 1-8 carbon atoms, a phenyl or benzyl group, X a halogen atom and η an integer from O - j5 mean; Compounds of the metals of group IV of the formula ^R 'm ^MX 4-m <"> where M is a metal of group IV of the periodic table with an atomic number of 14-72, and when M is a metal of group IVa, R ^{1 represents} an alkyl group with 1-8 carbon atoms, an alkoxy group with 1-8 carbon atoms, a phenyl or benzyl group, and if 209820/1030 M represents a Group IVb metal, R 'represents one Alkoxy group having 1-8 carbon atoms and X represents a halogen atom and m represents an integer of 0-4; and Tin dihalides of the formula SnX ₂ (iii) in which X is a halogen atom. J5.) Method according to Claim 1 or 2, characterized in that that an aluminum trichloride of the formula (i) with η = O as a reactant I and a compound of the formula (1) in which R "is an alkyl group having 1-12 carbon atoms or a halogenated alkyl group having 1-12 carbon atoms can be used as reactant II. 4.) Process according to claim 1 or 2, characterized in that a Tetrahalqgenid ejnes metal of group IV of the formula (ii), where M is Ti, Zr, Hf or Sn and m = 0, as reactants I and a compound of the formula (1) in which R "is an alkyl group having 1-12 carbon atoms or a halogenated alkyl group having 1-12 carbon atoms can be used as reactant II. 5.) The method according to claim 1 or 2, characterized in that a tin dihalide of the formula (iii), wherein X is a chlorine or Bromine atom denotes as reactant I and a compound of the formula (1) in which R "is an alkyl group with 1-12 Carbon atoms or a halogenated alkyl group having 1-12 carbon atoms is used as reactant II will. 6.) Method according to claim 3, characterized in that the compound of formula (1) as reactant II is replaced by the combination of group (12) in which phosphorus oxyhalide of the formula POX- ,, wherein X is a halogen atom, as a compound containing a phosphorus halogen bond, in Combination with the P-O-C bond-forming component, namely- 209820/1030 borrowed an aliphatic alcohol with 1-12 carbon atoms, is selected. 7.) The method according to claim k, characterized in that the compound of formula (1) is replaced as re action participants II by the combination of group (12) in which phosphorus oxyhalide of the formula POX ^, (in which X is a halogen atom) as a compound having a phosphorus halogen bond is used in combination with the POC bonding component of an aliphatic alcohol having 1-12 carbon atoms. 8.) The method according to claim 5 *, characterized in that the compound of formula (1) is replaced as reactant II by the combination of group (12), wherein phosphorus oxyhalide of formula POX _V (wherein X is a halogen atom) as a compound that contains a phosphorus halogen bond, is used in combination with the P-O-C bond-forming component of an aliphatic alcohol having 1-12 carbon atoms. 9.) Method according to claim 1 or 2, characterized in that that the reaction product of a combination of compounds of different metals, such as aluminum alcoholates of the formula (i), where R is an alkoxy group with 1-8 carbon atoms and η = j5 mean, and Siliciumhaologenid or AlkylsiüicJum.halogenid der Formula (ii), in which M is Si and m is 0-2, as reactant I with the compound of the formula (1) in which R "is a Alkyl group with 1-12 carbon atoms or a halogenated alkyl group with 1-12 carbon atoms is used as reactant II as a catalyst. 10.) The method according to claim 9, characterized in that as reactant II the compound of formula (1) is replaced by the combination of group (12) in which phosphorus oxyhalide of formula POX-, (in which X is a halogen atom) as a compound, which has a phosphorus halogen bond, is used in combination with the P-O-C bond-forming component, an aliphatic alcohol having 1-12 carbon atoms. 209820/1030 11.) Process according to claim 1 or 2, characterized in that the reaction product is a combination of compounds of different metals, such as silicon halide and alkyl silicon halide of the formula (ii), wherein M is Si and m O - 2, and tin halide, alkyl and phenyl tin halides of the formula (ii), in which M is Sn and m is O -3 , as reactants I with the compound of the formula (1) in which R "is an alkyl group having 1-12 carbon atoms or a halogenated alkyl radical having 1-12 carbon atoms , is used as reactant II as a catalyst. 12.) The method according to claim 11, characterized in that the compound of formula (1) as a reactant II by the combination of group (12) in which phosphorus oxyhalide of the formula P0} U (in which X is a halogen atom) is replaced as Compound containing a phosphorus halogen bond in combination with the P-O-C bond-forming component of an aliphatic Alcohol with 1-12 carbon atoms is used. IJ.) Method according to claim 9 * characterized in that a combination of the reaction product of reactants I and II with a promoter selected from the organometallic Compounds of the following formulas (a) to (c), i.e. organoaluminum compounds of the formula R "" _p AlX _{> p} (a) where R "" is an alkyl group having 1-8 carbon atoms or the phenyl group, X is a halogen atom and ρ is an integer from 1-5 mean} organic zinc compounds of the formula Q ₂ Zn (b) wherein Q is an alkyl group having 1-4 carbon atoms or a phenyl group; and organomagnesium compounds of the formula 209820/1030 wherein Q has the meaning given above, is used as a catalyst. 14.) The method of claim 13> characterized in accordance that the quantitative ratio of the promoter to the reaction product as the main catalyst in the range of 0.01 - lies% - lOO wt.. 15 ·) Process according to claim 10, characterized in that a combination of the reaction product of the reactants I and II with a promoter selected from the organometallic compounds of the following formulas (a) to (c), i.e. organoaluminum compounds of the formula _- P (a) wherein R ' ^{m is} an alkyl group having 1-8 carbon atoms or a phenyl group, X is a halogen atom and ρ is an integer of 1-3; Organozinc compounds of the formula Q ₂ Zn ..: (b) wherein Q is an alkyl group having 1-4 carbon atoms or a phenyl group; and organomagnesium compounds of the formula (c) wherein Q has the meaning given above, is used as a catalyst. 16) The method according to claim 15, characterized in that the quantitative ratio of the promoter to the reaction product as the main catalyst in the range of 0.01 - 100 weight -.% Is. 209820/1030 17.) Method according to claim 11, characterized in that a combination of the reaction product of reactants I and II with a promoter selected from the organometallic Compounds of the following formulas (a) to (c), i. organoaluminum compounds of the formula _ _p (a) wherein R "" is an alkyl group having 1-8 carbon atoms or a phenyl group, X is a halogen atom and ρ is a whole Number from 1-5; organozinc compounds of the formula Q ₂ Zn (b) wherein Q is an alkyl group having 1 - k carbon atoms or a phenyl group; and organomagnesium compounds of the formula Q ₂ Mg (c) wherein Q has the meaning given above, is used as a catalyst. 18.) The method according to claim 17 ι characterized in that the quantitative ratio of the promoter to the reaction product as the main catalyst in the range of 0.01-100 wt. % . 19.) The method according to claim 12, characterized in that a combination of the reaction product of reactants I and II with a promoter selected from the organometallic Compounds of the following formulas (a) to (c), i. organoaluminum compounds of the formula R "» _p AlX _{> p} (a) 20982071030 wherein an alkyl group with 1-8 carbon atoms or is a phenyl group, X is a halogen atom and p is an integer of 1-3; organozinc compounds of. Formula Q ₂ ^Zn wherein Q represents an alkyl group having 1-4 carbon atoms or a phenyl group; and organomagnesium compounds of the formula QpMg (c) where Q has the same meaning as above, is used as a catalyst. 20.) Process according to claim 19 , characterized in that the quantitative ratio of the promoter to the reaction product as the main catalyst is in the range from 0.01 to 100% by weight. 21.) Process according to claim 1 or 2, characterized in that the reaction product of phosphorus trihalide of the formula PX ₇ (in which X is a halogen atom) among the halogen-containing phosphorus compounds of group (11) as reactants II "with aluminum trialkoxide of the formula (i) , wherein m = J> , is used as reactant I as a catalyst. 22.) Method according to claims 9, 10, 13 and 14, characterized characterized in that an aromatic hydrocarbon is used as a solvent for the homopolymerization of epichlorohydrin or the copolymerization of epichlorohydrin is used with other alkylene oxides. 23.) Process according to claims 9, 10, 13 and 14, characterized in that an aliphatic or alicyclic hydrocarbon • hydrogen as a solvent for the homopolymerization of epichloro 209820/1030 hydrin or for the copolymerization of epichlorohydrin with other alkylene oxides. 24.) Catalytic composition for homo- or mixed polymerization of vicinal alkylene oxides, the product of at least one of the following reactants I from the reaction of formulas (i) to (iii): (l) Aluminum compounds of the formula _n (i) where R is an alkyl, alkoxy or aryl group, X is a halo genatom and η represent an integer from 0-3; Group IV metal compounds of the formula wherein M is a metal of group IV of the periodic table with atomic numbers from 14-72, in which, when M is a metal of group IVa, R ^{1 is} an alkyl, alkenyl, alkoxy, aryl or aralkyl group, and when M represents a metal of Group IVb, R ^{1 represents} an alkoxy group, X represents a halogen atom and m represents an integer of Ö-4; and Tin dihalides of the formula SnX ₂ (iii) where X is a halogen atom, with at least one reactant II, composed of the phosphorus-containing compounds of the following 12 groups: (II) (1) (R ¹¹ O) ₃ PO (1) where R "is hydrogen, an alkyl group with 1-12 carbon atoms, a halogenated alkyl group with 1-12 carbon atoms, an alkenyl group with 1 - 12 carbon atoms - 209820/1030 atoms or a cycloalkyl group with 5-7 carbon (Or
Substance atoms which may contain alkyl "^ alkenyl sideboards with 1-4 carbon atoms, in which at least one of the groups R" is an organic radical from the above group and the other groups R "can optionally be identical or different; (2) Z (R ¹¹ O) ₂ PO (2) wherein R "has the same meaning as that given for formula (" I) and Z is an alkyl group with 1-8 carbon atoms or is an ary! group; (5) Z ₂ (R ¹ "O) PO (5) wherein R " ¹ has the same meaning as the meaning given in formula (1) with the exception of hydrogen and Z has the same meaning as Z of the formula (2), it being possible for the further groups Z to be identical or different; (4) (R "0) ₂ P-0-P (0R") ₂ . (4) δ ö wherein R "has the same meaning as the group R" of the formula (1); (5)? ^R "(R ¹¹ O) ^ POPOP (OR") _o (5) 0 0 0 wherein R "has the same meaning as the group R" of the formula (1); (6) OR "OR" Z-P-O-P-Z (6) f! Il 0 0 wherein R "and Z each have the same meanings as the group R" of the formula (1) or the group Z of Formula (2), where the further groups Z are optionally identical or different; 209820/1030 (7) (R ¹¹ O) ₃ P (7) wherein R "has the same meaning as the group R" of the formula (1); (8) Z (R ¹¹ O) ₂ P (8) wherein R "and Z each have the same meaning as the group R" of the formula (1) or the group Z of Formula (2); (9) Z ₂ (R ¹¹ O) P (9) in which R ^IM and Z each have the same meaning as the group R ^{m of} the formula (3) or the group Z 'of the formula (2), where the further groups Z may optionally be identical or different; (10) (R ¹¹ O) ₂ POP (OR ") ₂ (10) wherein R "has the same meaning as the group R" of the formula (1); (11) halogen-containing phosphorus compounds such as phosphorus oxyhalides and phosphorus halides, or a combination of any of the above halogen-containing phosphorus compounds with water; and (12) Combination of a phosphorus compound, such as phosphorus oxide, or compounds that have a phosphorus-halogen bond, with an aliphatic alcohol with 1 - 12 Koh-. carbon atoms, with an aliphatic polyvalent Alcohol with 1-12 carbon atoms, with epoxides derived from olefins with 2-12 carbon atoms, or dialkyl ethers having 4-8 carbon atoms, provided that when the dialkyl ether is used, phosphorus oxide is used as the phosphorus compound, the constituents are the esters of phosphorusoxyacids or the P-O-C bond as reaction products form, 209820/1030 provided that if a metal compound is the reactant I used a halide or a halogenated alkoxy connection is used, and if several metallic connections are used, at least one of the metallic connections Compounds should contain halogen, and if a halogen-containing phosphorus compound of group (11) of the reactant II or a combination of these with V / water is used, one or more alcoholates, such as alcoholates of the formula (i), where η = 5 *. and alcoholates of the formula (ii), in which η = 4, be used as reactant I is. 25.) Catalyst according to claim 24, characterized in that he from the reaction product, in which a combination of several compounds of different metals as reactants I is used, at least one of the metal compounds containing halogen, and a promoter selected from the group of compounds of the following formulas (a) to (c), i.e. alumiumorganischenVerbindungen the formula ^R "" p ^Alx 3-p ^<a> wherein R "" is an alkyl group having 1-8 carbon atoms or a phenyl group, X a halogen atom and ρ a whole Number from 1 - j5; organic zinc compounds of the formula Q ₂ Zn (b) wherein Q represents an alkyl group having 1-4 carbon atoms or a phenyl group; and organomagnesium compounds of the formula Q ₂ Mg (c) wherein Q has the meaning given above. 209820/1030